Iodine-containing anionic sanitizers

ABSTRACT

This invention is directed to iodine-containing compositions and their use as sanitizing compositions in dilute aqueous solution. The new compositions are iodinated polyalkylene oxide glycol monoesters of 5 or 6-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid.

United States Patent [1 1 Turney 5] Nov. 4, 1975 IODINE-CONTAINING ANIONIC 3,355,386 11/1967 Cantor et al. 424/150 S TI 3,513,098 5/1970 Cantor et 111.... 424/150 3,728,449 4/1973 Cantor et al.... 424/150 Inventor: George Holbrwk y, g Of 3,751,562 8/1973 Nichols 6. 424/150 Prussia, Pa. 3,753,968 8/1973 Ward 260/5l4 K [73] Assignee: Pennwalt Corporation, Philadelphia,

Pa. Primary Examiner-Albert T. Meyers Assistant ExaminerD. W. Robinson [22] Ffled July 1974 Attorney, Agent, or Firm-Robert G. Danehower [21] Appl. No.: 492,668

[ ABSTRACT This invention is i d to i di e-containing compo- [58] d 424 1 O 80 sitions and their use as sanitizing compositions in dile o are 5 lute aqueous solution. The new compositions are iodinated polyalkylene oxide glycol monoesters of 5 or 6- [56] References Clted carboxy-4-hexyl-2-cyclohexene-l-octanoic acid.

UNITED STATES PATENTS 3,081,232 3/1963 Powers et al. 424)1s0 11 m N0 D'awmgs 3 ,9 l 7 ,822 1 y 2 IODINE-CONTAINING ANIONIC SANITIZERS DETAILED DESCRIPTION OF INVENTION The C-2l dicarboxylic acid is obtained by reacting BRIEF DESCRIPTION OF NVENTION linoleic acid with acrylic acid in the presence of iodine lodophors are well known to require acidic aqueous 5 catalyst as disclosed in U.S. Pat. No. 3,753,968. The

solutions to maintain the stability of the iodine com- C-2l dicarboxylic acid is marketed under the tradeplex. An iodophor is defined as a mixture of iodine and mark DlACID. an iodine carrier which forms an iodine complex having The C-2l dicarboxylic acid is then esterified with the ability to increase the iodine solubility and stability polyalkylene oxide glycol by methods well known in in aqueous solution, the aqueous solution of complexed the chemical arts. Typically, the C-21 dicarboxylic acid iodine having germicidal properties. Phosphoric acid and the polyalkylene oxide glycols are mixed together and hydroxy acetic acids have been widely used for this under an inert atmosphere such as nitrogen with agitapurpose in preference to mineral acids in order to protion while heating to about 210C. Catalyst such as divide iodophor stability and have a composition which is butyl tin oxide and triphenyl phosphate may be used. not corrosive and which is not irritating to the hands or The reaction is terminated by cooling the reaction mass to a cows udder. when the acid number falls to the theoretical number I have now discovered a new iodophor composition desired. The liquid reaction mass is then usually filwhich is effective in maintaining iodine stability in tered.

aqueous solution without the necessity of adding acid The most reactive carboxylic acid is at the end of the to the solution. The new compositions are iodinated C alkyl chain and the monoester of the acid is formed polyalkylene oxide glycol monoesters of C-21 dicarat this point. Temperatures considerably higher than boxylic acid having the formula 5 or 6-carboxy-4-hexabout 200C must be employed before esterification yl-2-cyclohexene-l-octanoic acid. These esters will be takes place with the carboxlyic group attached to the referred to in this application for convenience as monocyclohexene portion of the molecule.

esters of C-21 dicarboxylic acid. These new iodine 25 The addition of the polyalkylene oxide chain to the complexes are effective iodine sanitizers. The new io- C-2l dicarboxylic acid by esterification forms the esdophors may be used in the food industry for sterilizing ters which are the basis for preparing the iodophors of milk and food processing equipment. They may also be this invention.

used with the addition of compatible detergents and The length of the polyalkylene oxide chain is not critsurfactants for cleaning and sterilizing food tanks and ical but it is important in determining the amount of iofood processing equipment. In dilute aqueous solution dine which can be complexed, the greater the chain my new iodophors are used to sterilize the hands of length, the more iodine can be held in the complex.

food processors or food servers and for sterilizing cows The length of the polyalkylene oxide chain will range udders after milking to control mastitis. between about 3 moles to about 34 moles. Preferably,

The basis of my new sanitizer is the C-21 dicarboxylic 35 the range will be about 6 to about 16 moles. The polyalcompound derived from fatty acids which can be ob kylene oxide chain can be added either as a polyethyltained by a process described in U.S. Pat. No. ene oxide glycol or as a polypropylene oxide glycol. 3,753,968 which is incorporated by reference. This di- Mixed chains of polyethylene and polypropylene oxide carboxylic acid forms the hydrophobic portion of the glycols are also suitable and the mixtures can either be detergent while the hydrophyllic portion is derived hetero mixtures or block-mixtures as described in U.S. from polyalkylene oxides at one of the carboxylic Pat. No. 3,355,386. These esters are designated as the groups. polyalkylene oxide glycol monoesters of C-21 dicar- These polyalkylene oxides are either ethylene oxide, boxylic acid having a mole ratio of polyalkylene oxide propylene oxide or mixed ethylene-propylene oxide glycol to C-2l dicarboxylic acid within the range of condensates. The chain length will range from about 3 about 1 to l to about 1 to 2 and in which ester the polymoles to about 34 moles of polyalkylene oxide. alkylene oxide glycol contains from about 3 to about 34 The iodinated complex is prepared by adding iodine moles of polyalkylene oxide as described above.

crystals to the monoesters of the C-21 dicarboxylic acid The monoesters of the C-21 dicarboxylic acid may be with mild agitation. The mixing is continued until all of represented by the following formulae depending on the iodine crystals have reacted. the mole ratio of polyalkylene glycol to C-2l dicarbox- The iodophor sanitizing compositions may then be ylic acid employed in the reaction:

prepared by adding water, sufficient solubilizer to put 1. Monoester of C-21 Dicarboxylic Acid 2 moles the iodine complex into solution and finally adjusting of C-21 Dicarboxylic Acid to 1 mole of Polyalkylene the pH for the desired end use by adding alkaline mate- Glycol rials. The iodinated C-2l monoesters may be formulated as concentrates providing about 1% to about 20% available iodine or higher. where R is ethylene oxide, propylene oxide or mixed The diluted iodophor solutions are effective germiethylene-propylene oxides in random distribution or cidal agents for such bacteria as salmanela typhosa and block groups, one X is hydrogen and the other X is carstaphylococcus aureus when tested by the AOAC boxylic, n is about 3 to about 34 and where R is ethylmethod. ene or propylene.

3 2. Monoester of C-21 Dicarboxylic Acid l to 1 mole ratio of Polyalkylene glycol to C-2l Dicarboxylic Acid where R is ethylene oxide, propylene oxide or mixed ethylene-propylene oxides in random distribution or block groups where one X is hydrogen and the other X is carboxylic and n is about 3 to about 34.

The type of ester represented by the above formulae is determined by the mole ratio used in the esterification reaction. If two moles of C-21 dicarboxylic acid per mole of polyalkylene oxide glycol then a reaction product is obtained having a major amount of the C-21 Dicarboxylic acid ester having the structure represented by formula 1. If a one to one mole ratio is used the reaction product is primarily the monoester of C-21 dicarboxylic acid represented by formula 2. Intermediate mixtures are obtained by adjusting the mole ratio between one and two.

The polyalkylene oxide glycol monoesters of the C-21 dicarboxylic acid represented in the above formulae are iodinated by adding iodine crystals to the monoester and then agitating the mixture until all of the iodine crystals have reacted. Gently warming the mixture will speed up the reaction. Since the C-21 dicarboxylic acid has an iodine number of 58, a portion of the iodine will react with the hydrophobic portion of the anionic surfactant. This iodine is not available iodine as that term is used in the industry to designate the iodine that is present as a complex with the alkylene oxide portion of the monoester. It is available iodine which provides the germicidal effect. The available iodine is determined by titration with sodium thiosulphate. The total iodine may be determined by combustion methods.

The amount of iodine added to the C-21 dicarboxylic monoester will depend on its end use. I have prepared concentrates containing from about 1 to about 47% by weight available iodine. The sanitizers for contact with the skin are usually at about 1% available iodine. Using the monoester of the C-21 acid which is the subject of this invention, I have been able to prepare concentrates containing as high as 47% by weight available iodine but they are' not generally used or sold in such a high concentration.

The iodine added to the monoester of the C-21 dicarboxylic acid to prepare concentrates will generally be at a weight ratio of about 0.05 to l to about 2 to l, preferably from about 0.1 to about 1.65 to 1 weight ratio of iodine to monoester.

The iodinated monoesters of the C-21 acid are only slightly soluble in water and a solubilizer is required to place them in solution and to maintain solubility while subject to the normal storage temperature variations. The solubilizers for iodophors are commonly called iodine solubilizers. The normal storage temperatures range from about F to about 100F. The amount of solubilizer required to place the iodinated monoesters of C-21 dicarboxylic acid in solution and to insure their solubility within the temperature range of about 30F to about 100F is designated as an effective amount of solubilizer. The ratio of solubilizer to iodinated mono- 4 ester of C-21 dicarboxylic acid will generally be within the range of about 0.3 to 1 to about 7.5 to 1.

The preferred solubilizers for placing the anionic iodinated monoesters of the C-21 dicarboxylic acid in aqueous solution in order to maintain the anionic character of this iodophor system are the anionic alkoxylated phosphate esters, the anionic alkoxylated sulfate esters and the anionic polyalkylene oxide glycol monoesters of C-21 dicarboxylic acid having a mole ratio of polyalkylene oxide glycol to C-2l dicarboxylic acid within the range of about 1 to 1 to about 1 to 2. The polyalkylene oxide glycol chains will generally contain from about 3 to about 34 moles of polyalkylene oxide. The alkoxylated phosphate esters and sulfate esters will generally have a polyalkylene oxide chain of from about 3 to about 34 moles of polyalkylene oxide.

The anionic phosphate esters suitable as solubilizers are the acid phosphate mono and diesters of hydroxylterminated polyalkoxide condensates and the complex phosphate ester-salts resulting from neutralization of these acid phosphate esters by a base. The hydrophobic portion of the phosphate ester may be alkanol group of about C to about C phenol or C to C alkyl substituted phenol. Sodium lithium and potassium hydroxides are the commonly used bases in preparing salts. The polyalkylene oxide chains will range from about 3 to about 34 moles of polyalkylene oxide and may be EO, P0 or mixed EO-PO polymers.

Examples of alkoxylated phosphate esters are the mono and diphosphate esters of alkoxylated phenol and alkylsubstituted phenol. The mono phosphate esters may be represented by the formula where n is about 3 to about 34. The diphosphate esters may be represented by the formula where n is about 3 to about 34. Alkyl substituents on the phenol molecule will range from C to C Phosphate esters ofalkoxylated alcohols are also suitable such as the monophosphate ester of hetero EO-PO (4 to 6.8/1) on the mixture of normal decyl and dodecyl alcohols and the monophosphate ester of butyl alcohol containing 6 moles of ethylene oxide.

The second class of anionic solubilizers are the alkoxylated sulfate esters containing about 3 moles to about 16 moles of polyalkylene oxide. The hydrophobic portion of the sulflate esters may be an alkanol group of about C to about C carbons or an aromatic group,

- preferably phenol or C to C alkyl substituted phenol.

Examples of suitable alkyoxylated sulfate esters are the alkoxylated sulfate esters of phenol and alkylsubstituted phenol. These esters may be represented by the formula where n is about 3 to about 34 and R is alkyl of 0 to about l6 carbons.

The third class of anionic alkoxylated surfactants useful as iodine solubilizers in my invention are the polyalkylene oxide glycol monoesters of C-21 dicarboxylic acid having a mole ratio of polyalkylene oxide glycol to C-21 dicarboxylic acid within the range of about 1 to 1 to about 1 to 2. The polyalkylene oxide chain will generally contain from about 3 to about 34 moles of polyalkylene oxide of the E0, PO and hetero EO-PO and block mixtures. Examples of these monoesters appear in Table 1.

Where it is not important to maintain the anionic character of the iodophor the iodinated monoesters of the C-21 dicarboxylic acid may be solubilized with the nonionic polyalkylene oxide surfactants. These nonionics will contain polyalkylene oxide polymer chains of about 3 moles to about 16 moles of polyalkylene oxide. Suitable nonionics are the ethoxylated, propoxylated or mixed EO-PO phenols, alkyl phenols, aliphatic alcohols, carboxylic esters and the block and hetero polyoxypropylene-polyoxyethylene copolymers. The alkyl substituent of the alkyl phenols and aliphatic alcohols will range from about C to C carbons. Octyl and nonyl phenol are typical alkyl phenols. Typical alcohols are octyl, decyl, dodecyl, cetyl, lauryl, oleyl, tridecyl and stearyl alcohol. Suitable carboxylic esters are the polyethylene glycol mono or diesters of'lauric, oleic, stearic, tall oil and ricinoleic acids. Polyoxyethylene fatty acid amides are also suitable nonionic solubilizers. The polyoxypropylene-polyoxyethylene block polymers sold under the Pluronic trademark by Wyandotte Chemicals are useful nonionic solubilizers for my iodophors.

It will be appreciated that more than one solubilizer can be used of a single class as well as a mixture of solubilizers from different classes. I have found that the ratio of solubilizer to iodinated monoester of C-21 dicarboxylic acid in my compositions will range from about 0.2 to about 20 on a weight basis.

Alcohols such as ethyl alcohol and glycols such as ethylene glycol or propylene glycol are known solubilizers for iodine complexes and may be used in conjunction with the polyalkylene oxide containing surfactants.

Concentrates containing from about 1 to about 47% available iodine are readily prepared by iodinating the polyalkylene oxide of the C-21 monoester, adding a solubilizer and if desired, water and an alkaline material to adjust the pH. Agitation of the materials will as sist in solubilizing the iodinated monoester. Suitable alkaline materials are trisodium phosphate, disodium phosphate, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, etc.

The pH of the concentrates and use solutions are always maintained on the acid side, generally within the range of about 4 to'about 6.5 since the iodine complexes are only stable in acid.'This assures a longer shelf life for the iodine formulations. The pH determinations are made with a pH meter.

The amount of water added to any particular solution or concentrate is not critical. 1 have found that the ratio of water to the iodinated monoesters of C-21 dicarboxylic acid in my concentrates may range from 0 to about 25 on a weight basis.

The iodinated compositions of this invention can be used as iodine sanitizers in food plants and dairies. The sanitizers derived from the iodinated monoester of the C-21 dicarboxylic acid are generally supplied as iodine solutions containing from about 1 about 1.75% available iodine in a water carrier. The food processor will then dilute it further with water at a concentration of from 12.5 to 500 ppm of available iodine to form the sanitizing solution. The sanitizers are always used as acidic solutions, generally at a pH of about 4 to about 6.5.

The sanitizing solution is applied to food processing tables, floors, walls and utensils. It can be applied by a spray, by fogging, by immersion of the article in the liquid sanitizing solution and it can be applied as a circulating-in-line sanitizer. Generally, the iodine sanitizer is applied after a cleaning operation using a detergent or a soap. The iodine sanitizing solution should be .in contact with the metal that is being sanitized for at least 2 minutes. The iodine sanitizers are used to ambient temperatures and should not be heated. Following the sanitizing treatment, the surfaces are generally rinsed with potable water.

The iodophor compositions are also used as a test dip after milking for mastitis control. For this use the sanitizer is diluted with water or it can be supplied as a prediluted solution of from about 5,000 to about 10,000 ppm of available iodine. At this concentration the iodine solution acts as a disinfectant. The solution is applied to the teat in a cup and the iodine solution is allowed to remain on the teat.

The iodophors of this invention can also be diluted with water to a concentration of from about 12.5 to about 500 ppm of available iodine for sanitizing the skin of humans and for sanitizing articles of clothing such as rubbers, boots and gloves.

The best mode of practicing my invention will be apparent from a consideration of the following examples.

EXAMPLE 1 Preparation of Monoesters The polypropylene oxide glycol monoester of the C-21 dicarboxylic acid was prepared by esterifying 1 mole of a polypropylene oxide glycol with 2 moles of C-21 dicarboxylic acid for 3 hours at 210C. in a nitrogen atmosphere. The reaction was monitored by periodic determination of the acid number. Dibutyl tin oxide and triphenyl phosphate at 0.5% concentration was used to catalyze the reaction. Following completion of the reaction, the liquid product was filtered to remove all solids.

Using the procedure outlined above, the following liquid polyalkylene oxide monoesters of the C-21 dicarboxylic acid were prepared: polyethylene glycol 4.5 moles, polyethylene glycol 9 moles, polypropylene glycol 8 moles, polyethylene glycol 13.5 moles .7 and polypropylene glycol to 13 moles. These monoesters have the formula represented by l on page 4. In the same manner, monoesters were prepared using 1 to 1 mole ratios of C-21 dicarboxylic acid and polyalkylene oxide glycol having the formula represented by 2 on page 6.

EXAMPLE 2 Iodination of Monoesters Table 1 8 EXAMPLE 3 Concentrates of Iodinated Monoester of C-21 Carboxylic Acid Concentrates of the iodinated monoesters of the C-21 dicarboxylic acid prepared as described in Example 2 are formulated by adding one or more of the solubilizing agents described above. The concentration of the iodine is regulated in a number of ways, for example, by the amount of iodine added to the monoester or by the amount of solubilizer, water and additive to control the pH. In general, an effective amount of the solubilizer used will be that amount required to put the monoester of the C-21 dicarboxylic acid in solution plus an additional amount to prevent phase separation if the temperature was to drop to about F. The pH additive, if needed, would be the alkaline materials previously described to bring the pH within the range of about 4.5 to about 6.5. Typical concentrates are shown in Table 2.

Iodinated Monoesters Polypropylene glycol (8 moles ppo.*) monoester of C-21 dicarboxylic acid (1 mole ppg*. to 2 moles Diacid) Iodine Polyethylene glycol (4.5 moles peo.*) monoester of C-21 dicarboxylic acid (1 mole ppg. to 2 moles Diacid) Iodine Polyethylene glycol (9 moles peo.) monoester of C-21 dicarboxylic acid (1 mole peg.* to 2 moles Diacid) Iodine Polyethylene glycol (13.5 moles peo.) monoester of C-21 dicarboxylic acid (1 mole peg. to 2 moles Diacid) Iodine Polypropylene glycol (10-13 moles of ppo.) monoester of C -2l dicarboxylic acid (1 mole ppg. to 2 moles Diacid) Iodine Polypropylene glycol (10-13 moles ppo.) monoester of C-21 dicarboxylic acid (1 mole ppg. to 2 moles Diacid) Iodine Available iodine 46.9%

Polyethylene glycol (13.5 moles peo.) monoester of C-21 dicarboxylic acid (1 mole peg. to 1 mole Diacid) Iodine Polyethylene glycol (13.5 moles peo.) monoester of C-21 dicarboxylic acid (1 mole peg. to 1 mole Diacid) Iodine ppo polypropylene oxide Pp P p py glycol peg polyethylene glycol peo polyethylene oxide 1. Polypropylene glycol (10l3 moles ppo.) monoester of grams grams grams grams grams grams grams grams grams grams grams grams grams grams grams grams Table 2 Concentrates grams (C,-, to C aliphatic alcohol approx. 6 parts of alcohol to 22 parts of mixed ethylene oxide-propylene oxide condensate) Table 2-continued Concentrates TOTAL 1000 grams (available iodine 4.4%) Sold by Wyandotte Chemicals 3. Polyethylene glycol (4.5 moles peo.) monoester of C-2l dicarboxylic acid (1 mole peg. to 2 moles diacid 135 grams Iodine 32 grams Disodium phosphate 13 grams Water 250 grams Plurafac D- solubilizer 570 grams TOTAL 1000 grams (available iodine 2.0%)

4. Polyethylene glycol (13.5 moles peg.) monoester of TOTAL 100 grams EXAMPLE 4 -continued H 2.0 3.2 5.1 Sanitizer Formulations p The iodophor sanitizer compositions are generally The available iodine of theabove formulation was marketed at 1 to 1.75% available iodine solutions. Typ- 25 1.56% when prepared and was 1.19' after five weeks ical sanitizer formulations are shown in Table 3. storage.

Table 3 Sanitizer Formulations 1. Polyethylene glycol (13.5 moles peo.) monoester of C-21 dicarboxylic acid (1 mole peg to 2 moles Diacid) 135 grams Iodine 28 grams Solubilizer Octyl phenol polyethylene oxide (11 moles of ethylene oxide) condensate 100 grams Water 737 grams TOTAL 1000 grams Additions to disodium phosphate alkaline material oxide) condensate v 170 grams Alkaline material (disodium phosphate) 13 grams Water 654 grams TOTAL 1000 grams were made to raise the pH within the range of about 4.5

After formulating the above concentrate the pH was to about 6.5. Flgures are in grams.

6.5 and the available iodine was 1.73% by titration with sodium thiosulphate; Four months later the pH was 5.7 and the available iodine was 1.4%. A sample of the Sanitizer 100 100 Disodium phosphate 0.4 0.8 1.2 I

lyzed 1.26% available iodine.

3. Polyethylene glycol (13.5 moles peo.) monoester of identical concentrate held at 100F for 4 months ana- C-2l dicarboxylic acid (1 mole peg to 2 moles Diacid) grams Iodine 14 grams Octyl phenol polyethylene oxide (1 1 moles of ethylene oxide) condensate 50 grams Water 847 grams vTOTAL 1046 grams I Available iodine 0.79%

4. Polyethylene glycol (13.5 moles peo.) monoester of C21,dicarboxylic acid (1 mole peg. to 2 moles Diacid) 135 grams Iodine 14 grams Disodium phosphate 8 grams Monosodium phosphate 3 grams Propylene glycol 20 grams Octyl phenol polyethylene oxide (11 moles of ethylene oxide) condensate 40 grams -continued Water 840 grams TOTAL 1060 grams Available iodine 0.46%

5. Polyethylene glycol (13.5 moles peo.) monoester of C-21 dicarboxylic acid (1 mole of peg to 1 mole Diacid) 10.5 grams Iodine 19.5 grams Solubilizer- 300 grams monophosphate ester of 3 mole ethoxylated phenol (Sold by Witco Chemical under Emcol TS 21 l trademark) Water 670 grams TOTAL 1000 grams Available iodine 1.27%

6. Polyethylene glycol (13.5 moles peo.) monoester of C-21 dicarboxylic acid (l mole of peg. to 1 mole Diacid) 10.5 grams Iodine 19.5 grams Solubilizer- 200 grams monophosphate ester of 9.5 mole ethyoxylated nonylphenol (Sold by Rohm & Haas under QS-3O trademark) Water 770 grams TOTAL 1000 grams Available iodine 1.27%

7. Polypropylene glycol (IO-l3 moles ppo.) monoester of C-21 dicarboxylic acid (l mole ppg. to 2 moles Diacid) 11.31 grams Iodine 18.69 grams Water 670 grams 300 grams each of the following solubilizers were added to separate batches of the above to complete the formulations: (a) sodium sulphate of nonylphenol poly (ethyleneoxy) ethanol (Sold under Alipal E 526 trademark by GAF Co.) Available iodine 1.27% (b) mono and diphosphate ester of 6 mole ethoxylated C to C normal alcohols (Sold under GafacGB-SZO trademark by GAF) Available iodine 0.83% (c) monophosphoric ester of 4 to 6.8 EO-PO on C to C, normal alcohols. Available iodine 1.27%

8. Polyethylene glycol (13.5 moles peg.) monoester of C-21 dicarboxylic acid (1 mole peg. to 1 mole of Diacid) 1 grams Iodine grams Solubilizer polyethylene glycol (13.5 moles peg.) 0 grams monoester of C-21 dicarboxylic acid (1 mole peg. to 1 mole of Diacid) Solubilizer monophosphate ester of 9.5 mole ethoxylated nonylphenol 2.0 grams Water 87.0 grams TOTAL 100 grams 9. Polyethylene glycol (13.5 moles peg.) monoester of C21 dicarboxylic acid (1 mole peg. to-l mole of diacid) 1.1 grams Iodine 1.9 grams Solubilizer polyethylene glycol (13.5 moles peg.) 8.0 grams monoester of C-21 dicarboxylic acid (1 mole peg. to 1 mole of Diacid) Solubilizer monophosphate ester of 9.5 mole 2.0 grams ethoxylated phenol water 87.0 grams TOTAL 100 grams EXAMPLE Germicidal Effectiveness The polypropylene glycol monoester of C-21 dicarboxylic acid concentrate 2 in Table 3, was evaluated for bacteriacidal effectiveness by the A.O.A.C. Available Chlorine Germicidal Equivalent Concentration Test, A.O.A.C. Methods of Analysis, 11th Ed. 1970, pages 63-64, and was found to be equal to sodium hy- 60 pochlorite. The available iodine of the Iodophor at 50,

and 12.5 parts per million was tested against a standard sodium hypochlorite solution of 200, 100, and parts per million of chlorine. Tests were made on two organisms: Salmanela typhosa, ATCC 6539 and Staphylococcus aureous, ATCC 6538. The results of this test shown in Table 4 indicate that the iodine sanitizer is bacteriacidally equivalent to the hypochlorite standard.

Table IV Bactericidal Effectiveness l. Salmanela Typhosa ATCC 6539 Available Chlorine Germicidal Equivalent Concentration Test Gennicide Concn. PPM Subculture Series NaOCl Control Concentrate 2 Table 3 50 Phenol Coefficient 5 mins 10 mins mins l-80 1-90 l-l00 2. Staphylococcus Aureous ATCC 6538 Available Chlorine Germicidal Equivalent Concentration Test Gennicide Concn. PPM. Subculture Series NaOCl Control Concentrate 2 Table 3 50 Phenol Coefficient 5 min 10 min 15 min l-6O l-7O l8O 2. The anionic iodophor composition of claim 1 in I Claim. which the polyalkylene oxide glycol is polypropylene l. The anionic iodophor composition consisting essentially of a polyalkylene oxide glycol monoester of 40 C-21 dicarboxylic acid represented by the structural oxide glycol containing from 10 to 13 moles of propylene oxide and the mole ratio of glycol to C-2l dicarboxylic acid is about 1 to about 2.

3. The anionic iodophor composition of claim 1 in which the polyalkylene oxide glycol is polyethylene oxide glycol containing about 9 moles of ethylene oxide and the mole ratio of glycol to C-2l dicarboxylic acid is about 1 to about 2.

4. The anionic iodophor composition of claim 1 in which the polyalkylene oxide glycol is polyethylene oxide glycol containing about 4.5 moles of ethylene oxide and the mole ratio of glycol to C-21 dicarboxylic acid is about 1 to about 2.

5. The anionic iodophor composition of claim 1 in which the polyalkylene oxide glycol is polyethylene oxide glycol containing about 13.5 moles of ethylene oxide and the mole ratio of glycol to C-21 dicarboxylic acid is about 1 to 1.

6. The anionic iodophor concentrate comprising the iodophor composition of claim 1 and an amount sufficient to put the said iodophor composition in aqueous solution of at least one iodine solubilizer selected from the group consisting of anionic alkoxylated phosphate esters, anionic alkoxylated sulfate esters and anionic polyalkylene oxide glycol monoesters of C-21 dicacarboxylic acid represented by the structural formula 15 y L 16 -c ontinued I continud or C/CH CH CH (CH H (CH2)7COO(R),.R' cH---c11 CH3(CH)5 CH /HC--(CH2),COO(R),,R' 5 L H CH H CH X i OOC(CH2), c c cn cn \CH-(IH /CH (K i X OOQCHZ)7 C C (CH2)5CHa where R is ethylene oxide, propylene oxide or mixed ethylene-propylene oxides in random distribution or block groups, X is hydrogen and the other X is carboxx x l 5 ylic, n is about 3 to about 34, R is ethylene or propylene, and having a mole ratio of polyalkylene oxide glywhere R is ethylene oxide, propylene oxide or mixed col to C-2l dicarboxlyic acid within the range of abou ethylene-propylene oxides in random distribution or 1 to l to about 1 to 2. block groups, X is hydrogen and the other X is carbox- 8. The iodophor concentrate comprising the iodoylic, n is about 3 to about 34, R is ethylene or p pyphor composition of claim 1 and a sufficient amount of lene, and having a mole ratio of olyalk l id l an anionic or nonionic iodine solubilizer to put the said col to C-2l dicarboxylic acid within the range of about iodophor COmPOSitiOH in aqueous IiO 1 t 1 t b t 1 t 2, 9. The iodine sanitizer composition comprising the 7, Th i i i d h concentrate comprising h iodophor concentrate of claim 6 and sufficient water to i d h composition f l i 5 d an amount ffibring the available iodine concentration of the sanitizer cient to put the said iodophor composition in aqueous mp f Withm F rang? of about "P 175% y solution of at least one iodine solubilizer selected from Welght 531d composltion havlng a P wlthln the range the group consisting of anionic alkoxylated phosphate of about about esters, anionic alkoxylated sulfate esters and anionic The lodlne Sanltller omposition comprising the polyalkylene oxide glycol monoesters of C-21 dicarloflophor concfantratei Q suiificleniw'fiter to boxylic acid represented by the structural formula bung the avallable lodme CQHCemYatIPH i' the range of about 1 to about 1.75% by weight, said composition having a pH within the range of about 4 to cu cH\H about 6.5.

11. The iodine sanitizer com osition com risin the Ma-m5 CH /C (CHZ)COO(R)"H 5 iodophor concentrate of claim and sufficiest wafer to bring the available iodine concentration within the X ,L range of about 1 to about 1.75% by weight, said composition having a pH within the range of about 4 to about 615. O1 40 l=v UNITED STATES TAZTEN'T OFTTQE QERTIFICATE QT @CEQTWN Patent No. 7, 822 Dated November 4, 1975 I t-5 George Holbrook Turney It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 66. "sulflate" should be sulfate-- Column 6, line 36, "test" should be --teat Table 2, line 9, "pl-l 4. 5%" should be pl-I -4., 5

Column 11, line 65, "bacterlaoldal" should be "bactericidal- Column 12, line 64, "Salmanela" should be "Salmonella-- Column 12, line 65, "aureous" should be --aureus= Column 12, line 67, "bacterlacidally" should be -=bacterloidally= a Table IV, line 2, "Salmanela Typhosa should be -Salmonella typhosa-== Table IV, line 20, "Aureous" should be -aureus-- {sum Anes'r:

RUTH C. MASON 6. MASMAM. DAMN Manning Officer (nmmissimver nj'kmems and Trademarks 

1. THE ANIONIC IODOPHOR COMPOSITION CONSISTING ESSENTIALLY OF A POLYALKENE OXIDE GLYCOL MONOESTER OF C-12 DICARBOXYLIC ACID REPRESENTED BY THE STRUCTURAL FORMULA
 2. The anionic iodophor composition of claim 1 in which the polyalkylene oxide glycol is polypropylene oxide glycol containing from 10 to 13 moles of propylene oxide and the mole ratio of glycol to C-21 dicaRboxylic acid is about 1 to about
 2. 3. The anionic iodophor composition of claim 1 in which the polyalkylene oxide glycol is polyethylene oxide glycol containing about 9 moles of ethylene oxide and the mole ratio of glycol to C-21 dicarboxylic acid is about 1 to about
 2. 4. The anionic iodophor composition of claim 1 in which the polyalkylene oxide glycol is polyethylene oxide glycol containing about 4.5 moles of ethylene oxide and the mole ratio of glycol to C-21 dicarboxylic acid is about 1 to about
 2. 5. The anionic iodophor composition of claim 1 in which the polyalkylene oxide glycol is polyethylene oxide glycol containing about 13.5 moles of ethylene oxide and the mole ratio of glycol to C-21 dicarboxylic acid is about 1 to
 1. 6. The anionic iodophor concentrate comprising the iodophor composition of claim 1 and an amount sufficient to put the said iodophor composition in aqueous solution of at least one iodine solubilizer selected from the group consisting of anionic alkoxylated phosphate esters, anionic alkoxylated sulfate esters and anionic polyalkylene oxide glycol monoesters of C-21 dicacarboxylic acid represented by the structural formula
 7. The anionic iodophor concentrate comprising the iodophor composition of claim 5 and an amount sufficient to put the said iodophor composition in aqueous solution of at least one iodine solubilizer selected from the group consisting of anionic alkoxylated phosphate esters, anionic alkoxylated sulfate esters and anionic polyalkylene oxide glycol monoesters of C-21 dicarboxylic acid represented by the structural formula
 8. The iodophor concentrate comprising the iodophor composition of claim 1 and a sufficient amount of an anionic or nonionic iodine solubilizer to put the said iodophor composition in aqueous solution.
 9. The iodine sanitizer composition comprising the Iodophor concentrate of claim 6 and sufficient water to bring the available iodine concentration of the sanitizer composition within the range of about 1 to 1.75% by weight, said composition having a pH within the range of about 4 to about 6.5.
 10. The iodine sanitizer composition comprising the iodophor concentrate of claim 7 and sufficient water to bring the available iodine concentration within the range of about 1 to about 1.75% by weight, said composition having a pH within the range of about 4 to about 6.5.
 11. The iodine sanitizer composition comprising the iodophor concentrate of claim 8 and sufficient water to bring the available iodine concentration within the range of about 1 to about 1.75% by weight, said composition having a pH within the range of about 4 to about 6.5. 